Hydroformylation method and catalyst using rhodium-ruthenium dual metal and tetradentate phosphine ligand

ABSTRACT

A homogeneous catalytic reaction method and a catalyst for isomerization and hydroformylation of long-chain internal olefins are disclosed. A rhodium-ruthenium metal complex is used as a catalyst; and the ligands are tetradentate phosphine ligands. By means of the catalytic system, homogeneous internal olefin isomerization aid hydroformylation can be performed under a certain temperature and pressure to obtain aldehyde products having high normal to iso ratios. The present invention is applicable to not only long-chain internal olefins (≥C8) but also internal olefins having a carbon number less than 8.

TECHNICAL FIELD

The invention relates to a method and a catalyst for isomerization andhydroformylation of internal olefins, in particular to a catalyticsystem with a rhodium-ruthenium dual metal complex combined with abiphenyl tetraphosphine ligand, and a method tor isomerization andhydroformylation of long chain internal olefins for a homogeneousreaction system.

BACKGROUND

The hydroformylation technique, also known as the “Oxo synthesis”, hasbeen one of the largest homogeneous reactions in the industrial sectorsince it was discovered by Often Roelen in 1938 (Chem. Abstr. 1944-3631)Each year, various aldehydes and alcohols produced from Fe, Zn, Mn, Co,Cu, Ag, Ni, Pt, Pd, Ri, Ru and Ir based catalysts have been over 10million tons. In these catalytic reactions, the ability to achieve highselectivity of linear products (i.e. high linear (normal) to branch(normal) ratio, or I/b) is extremely important for industrialapplications. Although large-scale chemical companies and researchinstitutes such as BASF, Dow, Shell, Eastman, LIKAT (Leibniz Institutefor Catalysis) and etc. have reported and patented such catalyticreactions in a large amount, linear selectivity is still a practicalproblem to be solved. New theories and methods for controlling linearselectivity are crucial for hydroformylation reactions. In particular,catalysts with high linear selectivity can produce chemicals in a moreenvironmentally friendly manner under mild conditions.

In industrial hydroformylation reactions, cobalt catalysts (e.g.HCo(CO)₄) are in a dominant position until the advent of rhodiumcatalyst (e.g., HRh(CO)₂(PPh₃)₃) in the 1970s. In 2004, it was estimatedthat approximately 75% of the hydroformylation reactions worldwide werebased on a rhodium-triarylphosphine catalyst system. The efficientselectivity of linear aldehyde products is critical in hydroformylationand its related reactions. The aldehyde product is also an importantintermediate in addition to chemicals such as perfumes. The furtherobtained aldehydes can be further hydrogenated, oxidized and animated tobe converted into alcohols, carboxylic acids and amines, and used inbulk chemicals, plasticizers, detergents, surfactants, various solvents,lubricants, coatings and other optical materials, etc.

The HRh(CO)(PPh₃)₂ catalytic system (J. Org. Chem., 1969, 34, 327-330)invented by Pruett and Smith at Union Carbide coordinates rhodium withan excess amount of phosphine ligands, to form an active and selectivehydroformylation species and successfully commercialized. TheHRh(CO)(PPh₃)₂ catalytic system requires a large amount of phosphineligand because the Rh-PPh₃ complex is easily decomposed in the catalyticsystem, and triphenylphosphine (PPh₃) lost from HRh(CO)(PPh₃)₂ will turnthe complex into more active but less selective complexes:HRh(CO)₂(PPh₃) and HRh(CO)₃. Therefore, taking 1-hexene as an example,in industrial process, it is necessary to use up to 820 times excess ofPPh₃ to Rh to ensure higher selectivity of linear to branched aldehydeproducts, wherein the selectivity is up to 17:1. In addition, theindustrial reaction of propylene uses a 400 times excess of PPh₃ to Rh,and the ratio of linear to branched aldehyde products is 8 to 9:1.

In the hydroformylation process, it is important to use less expensivestarting materials as reactants. For example, 2-octene and 3-octene areideal starting materials for the conversion of long-chain internalolefins to linear aldehydes. Raffinate II (a mixture of butenes andbutane) or a mixture of 1-butene and 2-butenes are the starting materialcommonly used in industrial hydroformylation reactions. Furthermore, thehydroformylation reaction of an olefin with functional groups such as ahydroxyl group (—OH) and a carboxyl group (—COOH) is also extremelyimportant. For example, the hydroformylation of propylene alcohol andthe subsequent reduction can produce 1,4-butanediol, which is animportant raw material for synthetic polymers and other derivatives. Inaddition, functionalized internal olefins can be used as anothersynthetic route for difunctionalized building blocks in polymersynthesis. For example, the product produced by the hydroformylation ofmethyl 3-pentenoate is a raw material in the synthesis of polyamides andpolyesters. In isomerization and hydroformylation reactions, highisomerization rate combined with high selectivity to form terminalaldehyde is an ideal reaction process, which not only reduce unnecessaryhydrogenation, but also reduce the probability of isomerization to otherconjugated compounds.

Many hydroformylation processes still utilize PPh₃ as ligands. Althoughthe rhodium/triphenylphosphine system has been successfully implementedin factories all over the world, it limits the ratio of normal toisomeric (n/i) aldehyde products to about 10:1. In addition, the largeamount of PPh₃ is not only poorly selective in the hydroformylationreaction, but also difficult in separation and posttreatment. In orderto tackle these problems, transition-metal-bisphosphorous chelatecomplexes have been reported and patented by research groups andcompanies throughout the world. For example2,2,-bis((diphenylphosphino)methyl)1, 1-biphenyl (Bisbi) invented byEastman; 6,6′-[3,) 3′-di-tert-butyl-5,5′-dimethoxy-1,1′-diphenyl-2-2′-diyl)bis(oxy)]bis(dibenzo[D,F] [1,3,2]diphophos)(Biphephos) by Union Carbide (Buckwald);4,5,-bisdiphenylphosphino-9,9-dimethylxanthene (Xantphos) and bidentateDiphosphoramidite by van Leeuween; 2, 2′-bis((diarylphosphino)methyl)-1,1-binaphthyl (Naphos) by Matthias Belter and etc. The structures ofthese bidentate phosphorus ligands are illustrated as follows:

Using the above bidentate phosphorous ligand, a 400 times excess of PPh₃can typically be reduced to only a 5 times excess of the chelatedbidentate phosphorous ligand. This chelated bidentate phosphorous ligandhas higher n/i (or I/b) ratio and catalytic activity in thehydroformylation reaction. For example, the n/i ratio of 1-hexenehydroformylation can be up to 70 to 120:1. Casey and van Leeuwenreported that the high selectivity with bisphosphorous ligand is due tothe formation of a large bite angle (120 degree) between transitionmetal and ligand, i.e The “Bite angle” theory, the structure isillustrated as follows:

Although there are many reports on the use of bidentate phosphorousligands for hydroformylation reactions, the development of higherselectivity and activity phosphorous ligands has been a research hotspotin the field of hydroformylation. However, it is difficult to achievehigh normal to iso products (n/i) ratio due to the detachment ofphosphorus during the coordination process of Rh-phosphorous complex andcarbon monoxide molecule. Therefore, the development of multidentatephosphorous ligand with multi-chelating and coordination abilities is ofgreat importance

In addition to high selectivity, high isomerization speed is also a veryimportant factor for the hydroformylation of internal olefins. Theisomerization catalyst used in the present invention:Carbonylchlorohydrido[-(di-tert-butylphosphinomethyl)-2-(N,N-diethylaminomethyl)pyridine]ruthenium(II), also known as Milstein Catalyst, its synthesis method androute was reported by the David Milstein (J. Am. Chem. Soc., 2005, 127.10840-10841). S. Perdriau et al. (Chem. Eur. J., 2014,47,15434-15442)reported the use of RuH(Cl)(PNN)(CO) catalysts for isomerization ofterminal olefins to internal olefins. These are the few reports on theisomerization of olefins with RuH(CI)(PNN)(CO) catalyst Besides, thereare few literatures on isomerization and hydroformylation to preparelinear aldehydes with rhodium-ruthenium dual metals.

Taking the 2-octenes hydroformylation as example, the Xantphos typeligand reported by van Leeuwen has a normal to iso products (n/i) ratioof 9.5 (Angew. Chem. Int. Ed, 1999. 38, 336) Beller reported a normal toiso products (n/i) ratio up to 10.1 with Naphos-type ligand (Angew.Chem. Int. Ed., 2001, 40, 3408). The linear selectivity ofortho-phosphonate ligand in the octene mixture was 2.2 claimed by Börner(Angew. Chem. Int. Ed., 2001, 40. 1696). The phosphinate ligands ofUnion Carbide Corp. (row Dow) have a normal to iso products ratio of:n/i=19 and 17 for 2-hexene and 2-octene respectively (U.S. Pat. No.4,769,498). All literatures and patents mention above used rhodium assingle metal catalyst.

The biphenyl tetradentate phosphine ligand (Tetrabi) used in the presentinvention has multiple chelating modes owing to its coordinationability. The hydroformylation of internal olefins is carried out inmulti-chelating coordination modes with Rh-Tetrabi complex. Phosphineligands are less likely to decompose from the Rh-Tetrabi catalystsystem, and the steric hindrance effect of phosphines inhibits theformation of the isomeric aldehyde product, so that a high normal to isoproducts ratio is easily obtained. Therefore, the present inventionutilizes a dual rhodium-ruthenium transition dual metals andmetal-biphenyl tetradentate phosphine ligand as a catalytic system toobtain an unprecedented high normal to iso products ratio in theisomerization and hydroformylation of long-chain internal olefins.

SUMMARY

In view of the shortcomings of the low normal to iso products ratio ofthe aldehyde products in the existing internal olefin hydroformylationcatalytic system, the technical problem to be solved by the presentinvention is to provide a catalyst which combines a rhodium-rutheniumdual metal with a tetradentate phosphine ligand, and a method ofhydroformylation of internal olefins. The catalytic system of theinvention has the advantages of high conversion rate, high normal to isoproducts ratio, stable catalyst at high temperature, and the etc.

The biphenyl tetradentate phosphine ligand according to the presentinvention, namely the chelating coordination mode of 2, 2′, 6,6′-tetrakis(diarylphosphinomethyl)-1,1′-biphenyl (Tetraphosphine, orTetrabi) and a transition metal rhodium, the structure is illustrated asfollows:

The present invention provides a novel catalyst for isomerization andhydroformylation of internal olefins, consisting of a rhodium complexand a ruthenium compound, is the rhodium complex is formed by completinga rhodium compound with a biphenyl tetraphosphosphine ligand.

The above catalyst, in which the molar ratio of the rhodium complex tothe ruthenium compound is ranged from 1:1 to 5:1, and the molar ratio ofthe biphenyl tetraphosphine ligand to the rhodium compound is rangedfrom 1:1 to 10:1.

The ruthenium compound may be Rhodium trichloride (RhCl₃), (bicyclo[2.2.1] hepta-2,5-diene) chloro rhodium (I) dimer ((Rh(NBD)Cl)₂), Chloro(1,5-cyclooctadiene) rhodium (I) dimer (Rh(COD)Cl)₂), Chlorodi(ethylene) rhodium dimer ((Rh(ethylene)₂CL)₂),Tris(triphenylphosphine) rhodium (RhCl(PPh₃)₃), Rhodium carbonylchloride ((Rh(CO)₂Cl)₂), Dicarbonylacetylacetonato rhodium (I)(Rh(acac)(CO)₂), acetylacetonato (1,5-cyclooctadiene) rhodium (I)(Rh(acac)(COD)), Rhodium carbonyl (Rd₆(CO)₁₆ or Rh₄(CO)₁₂), Rhodiumacetate (II) (Rh₂(OAc)₄), Rhodium(III) nitrate (Rh(NO₃)₃ or otherappropriate rhodium compound, preferably Dicarbonylacetylacetonatorhodium (I).

In the hydroformylation reaction, the concentration of the rutheniumcompound is ranged from 50 to 1,500 ppm, and preferably from 100 to 800ppm.

The organophosphine ligand has a monophosphine ligand such as triphenylphosphine (PPh₃) triphenyl phosphinate (P(OC₆,H₅)₃), etc., and mayalso be a polydentate phosphine ligand such as 2,2′-di((dipbenylphosphino)methyl)-1,1′-biphenyl (Bisbi),2,2′,6-tris(diphenylphosphinomethyl)-1, 1′-biphenyl (Tribi).2,2′-bis((diarylphosphino)methyl)-1, 1-binaphthyl(Naphos),4,5,-bisdiphenylphosphino-9,9-dimethyloxaxime(Xantphos), 6,6′-[(3,3′-di-tert-butyl-5,5′-dimethoxy-1,1′-diphenyl-2, 2′-diyl) bis(oxygen))]bis[D, F][1,3,2]diphosphine dioxane) (Biphephos). 2,2′6,6′,4-tetrakis(diphenylphosphinomethyl)-1, 1′-Biphenyl (Tetrabi) or othersuitable phosphine source. Wherein the biphenyl tetraphosphine ligandused in the present invention, namely: 2,2′,6,6′-tetrakis(diarylphosphonatemethyl-1, 1′-biphenyl (Tetrabi), has theoptimal hydroformylation effect and a very high ratio of normal to isoproducts when compared with the above phosphine ligands. The structureof the compound and its derivatives is illustrated as follows:

In the formula II, Ar may be benzene, m-trifluoromethylbenzene,3,5-ditrifluoromethylbenzene, p-methylbenzene, p-trifluoromethylbenzene,3,5-difluorobenzene, 3,5-dimethylbenzene, 3,5-di-tert-butylbenzene,3,5-di-tert-butyl-4-methoxybenzene, p-methoxybenzene,p-dimethylaminobenzene, 2-pyridine, p-fluorobenzene, 2, 3, 4, 5,6-pentafluorobenzene, tert-butyl, pyrrole and indole, the structures ofwhich are as follows:

The ruthenium compound may be ruthenium carbonyl (Ru₃(CO)₁₂), rutheniumtrichloride (RuCl₃), tris(triphenylphosphine) ruthenium (II) chloride(RuCl₂(PPh₃)₃), dichloro Tricarbonyl ruthenium dimer ((RuCl₂(CO)₃)₂),tris(triphenylphosphine)carbonylindoline (II) (RuH₂(CO)PPh₃)₃),(1,5-cyclooctane Ethylene ruthenium(II) dichloride ((RuCl₂(COD)_(n)),bis-(2-methylallyl)cyclooctane-1,5-dienyl ruthenium(Ru(COD)(methallyl)₂), Carbonylchlorohydrido[6-(di-tert-butylphosphinomethyl)-2-(N,N-diethylaminomethyl)pyridine]ruthenium (II),Carbonylhydrido[6-(di-t-butylphosphinomethylene)-2-(N,N-diethylaminomethyl)-1,6-dihydropyridine] ruthenium (II) (RuH (PNN) (CO)) or other appropriate rutheniumcompounds Preferably, Carbonylchlorohydrido[6-(di-tert-butylphosphinomethyl)-2-(N,N-diethylaminomethyl)pyridine]ruthenium (II) (RuH(Cl)(PNN)(CO)).

In the isomerization and hydroformylation reaction, the concentration ofthe ruthenium compound is ranged from 10 to 2000 ppm. and 100 to 1000ppm is preferred.

The preparation method of the internal olefin isomerization andhydroformylation catalyst of the present invention is as follows:

Stirring the weighted rhodium catalyst precursor and the biphenyltetradentate phosphine ligand at room temperature for 30 to 90 min in anorganic solvent under inert gas protection (anhydrous and deoxygenatedcondition); and then add the ruthenium catalyst into the rhodium-ligandcomplex solution and stirring at room temperature for 15 to 30 min.

The steps of the olefin isomerization and hydroformylation experimentsof the present invention under the rhodium-ruthenium dual metal andbiphenyl tetraphosphine ligand catalytic system are: first, under inertgas protection, transferring certain amount of the completedrhodium-ruthenium catalyst solution, certain amount of internal standardn-decane and isopropanol as an additive, certain amount of solvent, andfinally the substrate-internal olefin into a reaction flask equippedwith a magnetic stirrer, after the transfer is completed, chargingcertain amount of CO and H₂ into the autoclave containing the reactionflask. The pressure ratio of hydrogen to carbon monoxide is between1.5:1 to 10;1, which is optimally 1:1, the total pressure is between 0.2MPa and 4 MPa, of which 0.4 MPa to 1 MPa is preferred; finally, at anoil bath temperature between 8° C. and 140° C. which is optimal at 120°C. to 140° C., reacting with stirring for 1 to 12 hours, preferably 1hour to 4 hours.

In the reaction process for the purpose of not evaluating the catalyticeffect, it is unnecessary to add an internal standard. With isopropanolas an additive, the ruthenium catalyst accelerates the isomerizationrate of internal olefins in isopropanol.

The internal olefin substrate used in the present invention is 2-octene(cis, trans mixture), and the composition of the cis, trans-2-octene isdetermined by gas chromatography, 19.5% of the mixture component iscis-2-octene, and 80.5% of the mixture component is trans-2-octene. Theratio of the amount of the rhodium-based compound to the reactant isbetween 0.005 and 0.15 mol %, and preferably 0.01 to 0.08 mol % Themolar ratio of the organic phosphine ligand to the rhodium-basedcompound is between 1:1 and 10:1, preferably 4:1 and 6:1.

The gas chromatography analysis method according to the presentinvention comprises the following steps: (1) preparing a mixed solutionof 2-octene (cis-mixed mixture) and n-decane in different concentrationratios, and calculating correction factor K of internal standard and 2octene (cis, trans mixture) by GC analysis; (2) analyzing by gaschromatography with RTX-5 as stationary phase, flame ionizationdetection, setting split ratio to 20, injection port temperature to 250°C., detector temperature to 260° C., column initial column temperatureto 60° C. keep for 8 minutes, and then raising to a column temperatureof 120-180° C. at a speed of 5° C./min, the above analytical method canensure complete separation of high boiling aldehyde products from thechromatogram column; (3) obtaining the linear aldehyde percentage byfinding the integral of the corresponding peak according to the peaktime of the aldehyde product n-nonanal (a-aldehyde) and 2-methyl octanal(β-aldehyde); (4) calculate the peak area according to the peak time ofthe reactant 2-octene (cis, trans mixture) and the internal standard,and calculate the conversion rate, the number of conversion, etc , andin combination with the correction factor.

The organic solvent applicable for the above catalytic reaction processmay be methylbenzene, dichloromethane, dichloroethane, hexane, ethylacetate, methanol, ethanol isopropanol, trifluoroethanol, dioxane,acetonitrile, tetrahydrofuran, etc. The alcohol solvent is particularlyeffective for the dual metal catalyst of the present invention.

Internal olefins applicable for the dual metal catalytic homogeneoussystem of the present invention, from C₄ to C₈ are: 2-butene, cis.trans-2-pentene. cis, trans-2-hexene. cis. trans-3-hexene, cis,trans-2-heptene, cis, trans-3-heptene, cis, trans-2-octene, cis,trans-3-octene, cis, trans-4-octene.

The catalytic system of the rhodium-ruthenium dual metal complexdescribed in the present invention combined with the biphenyltetraphosphine ligand has an unprecedented high normal aldehyde toisomeric aldehyde ratio, high conversion rate (high conversion number),stable catalyst at high temperature and industrial amplification, etc,when compared with the hydroformylation reaction results of long-chaininternal olefin (≥C₈) in all literatures and patents domestic andabroad.

Since internal olefins are more prone to produce by-products such asbranched aldehydes and branched paraffins than end olefins, and thehydroformylation effect is more complicated, the aldehyde products arerelatively low in normal to iso product ratio. The industriallarge-scale hydroformylation process utilizes low-cost mixed internalolefins and terminal olefins as olefin feedstocks, wherein there aremore internal olefins and fewer terminal olefins, so the method providedby the present invention has greater industrial application value.

DESCRIPTION OF THE EMBODIMENTS

The following description is of preferred embodiments by way of exampleonly and without limitation to the combination of features necessary forcarrying the invention into effect. However, it should be noted that thepresent invention is by no means limited or restricted to the belowdescribed embodiments and the implementation features thereof butcomprises further modifications of the embodiments, in particular thosethat are comprised by modifications of the features of the describedexamples and/or by combination of one or more features of the describedexamples on the basis of the scope of protection of the independentclaims.

Example 1; Isomerization and hydroformylation (S/C=2000, S/C is themolar ratio of reactant to catalyst) using rhodium-ruthenium dual metal(Rh (acac) (CO)₂ RuH (CI) (PNN) (CO)) and biphenyl triphosphine ligand(Tribi), rhodium-ruthenium (Rh(acac)(CO)₂, RuH(Cl)(PNN)(CO)) andbiphenyl tetraphosphine ligand (Tetrabi)

Rh, Ru+Tribi: Weighing the catalyst Rh(acac)(CO)2 (5.2 mg, 0.02 mmol)and 2,2′, 6-tris(diphenylphosphinomethyl)-1, 1′-Biphenyl (Tribi) (60 mg,0.08 mmol) with a glove box into a complex flask, and then placing thedeoxygenated/dewatered dichloromethane (2.65 g, 31.2 mmol) solvent intoa flask, stirring to dissolve them to obtain a complex of rhodium andbiphenyl triphosphine ligand. Subsequently, weighing a rutheniumcatalyst RuH(Cl)(PNN)(CO) (9.8 mg, 0.02 mmol) with a glove box, addingit to the complexed rhodium catalyst solution, and stirring at roomtemperature to dissolve them. Placing the autoclave into the glove box,using a micro syringe to transfer 100 μl of the complexedrhodium-ruthenium catalyst solution into a reaction flask (5 ml) withmagnetic stirrer, and adding 100 μl of the internal standard n-decane,150 μl of additive, 350 μl of solvent and 2-octene (cis, trans mixture)(224.4 mg. 2 mmol). Then, taking the autoclave containing the reactionflask out from the glove box, and replacing the high-purity argon gas inthe vessel with H2 three times, raising the total pressure of theautoclave to 4 bar at a CO/H2 pressure ratio of 1:1, and then placingthe autoclave at oil bath temperature 140° C. and stirring for 1 hourand 4 hours, respectively.

Rh, Ru30 Tetrabi: Weighing the catalyst Rh(acac)(CO)2 (5.2 mg, 0.02mmol), 2, 2′, 6, 6′-tetrakis(diphenylphosphinomethyl)-1, 1′-biphenyl(Tetrabi) (76 mg. 0.08 mmol) with a glove box and placing them into acomplex flask, then adding deoxygenated/dewatered (2.65 g. 31.2 mmol)into the flask and stirring to dissolve them to obtain a complexsolution of rhodium and biphenyl tetraphosphine ligand. Subsequently,weighing the ruthenium catalyst RuH(Cl)(PNN)(CO) (9.8 mg, 0.02 mmol)with a glove box and adding it into the complexed rhodium catalystsolution, stiring at room temperature to dissolve them Placing theautoclave into the glove box, using a micro syringe to transfer 100 μlof the complexed rhodium-ruthenium catalyst solution into a reactionflask (5 ml) with magnetic, stirrer, and adding 100 μl internal standardn-decane, 150 μl additive and 350 μl solvent, and finally 2-octene (cis,trans mixture) (224.4 mg, 2 mmol). Then, taking the autoclave containingthe reaction flask out from the glove box, and replacing the high-purityargon gas in the vessel with three rimes, raising the total pressure ofthe autoclave to 4 bar at a CO/H2 pressure ratio of and then placing theautoclave at oil bath temperature 140° C. and stirring for 1 hour and 4hours, respectively.

TABLE 1

L/Rh Time Conversion l/b Linearity No. solvent ligand L/Ru [h] rate[%][%] [%] TON  1 ethanol Tribi 4:1 1 39.7 31.3 96.9 7.9 × 10²  2 ethanolTribi 4:1 4 78.6 34.7 97.2 1.6 × 10³  3 ethanol Tetrabi 4:1 1 68.8 65.898.5 1.4 × 10³  4 ethanol Tetrabi 4:1 4 87.2 43.9 97.8 1.7 × 10³  5methanol Tribi 4:1 1 53.8 61.8 98.4 1.1 × 10³  6 methanol Tribi 4:1 481.3 46.8 97.9 1.6 × 10³  7 methanol Tetrabi 4:1 1 79.6 82.3 98.8 1.6 ×10³  8 methanol Tetrabi 4:1 4 90.8 60.0 98.4 1.8 × 10³  9trifluoroethanol Tribi 4:1 1 61.2 69.4 98.6 1.2 × 10³ 10trifluoroethanol Tribi 4:1 4 78.7 58.6 98.3 1.6 × 10³ 11trifluoroethanol Tetrabi 4:1 1 73.6 141.9 99.3 1.5 × 10³ 12trifluoroethanol Tetrabi 4:1 4 93.6 61.6 98.4 1.9 × 10³

Example 2: Isomerization and hydroformylation (S/C=4000) usingrhodium-ruthenium dual metal (Rb(acac)(CO)₂RuH(Cl)(PNN)(CO)) andbiphenyltriphosphine ligand (Tribi), rhodium-ruthenium dual metal (Rh(acac)(CO)₂, RuII(Cl)(PNN)(CO)) and biphenyl tetraphosphine ligand (Teirabi)

Rh, Ru+Tribi: Weighing the catalyst Rh(acac)(CO)₂ (2.6 mg, 0.01 mmol),2, 2′, 6-Tris(diphenylphosphinomethyl)-1,1′-biphenyl (Tiibi) (30 mg,0.04 mmol) within a glove box and placing them into a complex flask,then adding deoxygenated/dewatered dichloromethane (2.65 g. 31.2 mmol)into the flask, and stirring to dissolve them to obtain a complexedsolution of rhodium and biphenyl triphosphine ligand. Subsequently,weighing the ruthenium catalyst RuH(Cl)(PNN)(CO) (4.9 mg. 0.01 mmol)within a glove box and adding it into the complexed rhodium catalystsolution at room temperature. Placing the autoclave into the glove box,using a micro syringe to transfer 100 μl of the complexedrhodium-ruthenium catalyst solution into reaction flask (5 ml) withmagnetic stirrer, and adding 100 μl of the internal standard n-decane,150 μl additive and 350 μl of solvent, and finally 2-octene (cis. transmixture) (224.4 mg. 2 mmol). Then, taking the autoclave containing thereaction flask out from the glove box, and replacing the high-purityargon gas in the vessel with H₂ three times, raising the total pressureof the autoclave to 4 bar at a CO/H₂ pressure ratio of 1:1, and thenplacing the autoclave at oil bath temperature 140° C. and stirring for 1hour and 4 hours, respectively.

Rh, Ru+Tetrabi; Weighing the catalyst Rh(acac)(CO)₂ (2.6 mg. 0.01 mmol).2, 2′, 6, 6′-tetrakis(diphenylphosphinomethyl)-1, 1′-biphenyl (Tetrabi)(38 mg, 0.04 mmol) within a glove box and placing them into a complexflask, then adding deoxygenated/dewatered dichloromethane (2.65 g, 31.2mmol) in a complex flask and stirring to dissolve them to obtain acomplex solution of rhodium and biphenyl tetraphosphine ligand.Subsequently, weighing the ruthenium catalyst RuH(Cl)(PNN)(CO) (4.9 mg,0.01 mmol) within a glove box and adding it into the complexed rhodiumcatalyst solution at room temperature. Placing the autoclave into theglove box, using a micro syringe to transfer 100 μl of die complexedrhodium-ruthenium catalyst solution into a reaction flask (5 ml) withmagnetic stirrer, and adding 100 μl of internal standard n-decane. 150μl additive and 350 μl solvent, and finally 2-octene (cis, transmixture) (224.4 mg. 2 mmol). Then, taking the autoclave containing thereaction flask out from the glove box, and replacing the high-purityargon gas in the vessel with H₂ three times, raising the total pressureof the autoclave to 4 bar at a CO/H₂ pressure ratio of 1:1, and thenplacing the autoclave at oil bath temperature 140° C. and stirring for 1hour and 4 hours, respectively.

TABLE 2

L/Rh Time conversion l/b Linearity No. solvent ligand L/Ru [h] rate[%][%] [%] TON  1 ethanol Tribi 4:1 1 17.6 13.7 93.2 7.0 × 10²  2 ethanolTribi 4:1 4 50.4 15.9 94.1 2.0 × 10³  3 ethanol Tetrabi 4:1 1 27.8 32.397.0 1.1 × 10³  4 ethanol Tetrabi 4:1 4 59.7 37.5 97.4 1.5 × 10³  5methanol Tribi 4:1 1 44.3 51.7 98.1 1.8 × 10³  6 methanol Tribi 4:1 465.0 32.5 97.0 2.6 × 10³  7 methanol Tetrabi 4:1 1 68.2 92.8 98.9 2.7 ×10³  8 methanol Tetrabi 4:1 4 81.4 78.0 98.7 3.3 × 10³  9trifluoroethanol Tribi 4:1 1 44.5 76.2 98.7 1.8 × 10³ 10trifluoroethanol Tribi 4:1 4 65.4 46.8 97.9 2.6 × 10³ 11trifluoroethanol Tetrabi 4:1 1 63.7 93.8 98.9 2.5 × 10³ 12trifluoroethanol Tetrabi 4:1 4 81.6 59.5 98.3 3.3 × 10³

Example 3: Isomerization and hydroformylation (S/C=10000) usingrhodium-ruthenium dual metal (Rb(acac)(CO)₂ RuH(Cl)(PNN)(CO)) andbiphenyl triphosphine ligand (Tribi), rhodium-ruthenium dual metal(Rh(acac)(CO)₂ , RuH(Cl)(PNN)(CO)) and biphenyl tetraphosphine ligand(Tetrabi)

Rh, Ru+Tribi: Weighing the catalyst Rh(acac)(CO)₂ (2.6 mg, 0.01 mmol),2, 2′,6-Tris(diphenylphosphinomethyl)-1,1′-biphenyl (Tribi) (30 mg, 0.04mmol) within a glove box and placing them into a complex flask, thenadding deoxygenated/dewatered dichloromethane (6.63 g, 78.0 mmol) in aflask and stirring lo dissolve them to obtain a complex solution ofrhodium and biphenyl triphosphine ligand. Subsequently, weighing aruthenium catalyst RuH(Cl)(PNN)(CO) (4.9 mg, 0.01 mmol) within a glovebox, adding it to the complexed rhodium catalyst solution, and stirringto dissolve them at room temperature. Placing the autoclave into theglove box, using a micro syringe to transfer 100 μl of the complexedrhodium-ruthenium catalyst solution into a reaction flask (5 ml) withmagnetic stirrer, and adding 100 μl of internal standard n-decane, 150μl of additive and 350 μl of solvent, and finally 2-octene (cis, transmixture) (224.4 mg, 2 mmol). Then, taking the autoclave containing thereaction flask out from the glove box, and replacing the high-purityargon gas in the vessel with H₂ three times, raising the total pressureof the autoclave to 4 bar at a CO/H₂ pressure ratio of 1:1, and thenplacing the autoclave at oil bath temperature 140° C. and stirring for 1hour and 4 hours, respectively.

Rh, Ru+Tetrabi: Weighing the catalyst Rh(acac)(CO)₂ (2.6 mg, 0.01 mmol).2,2′, 6, 6′-tetrakis(diphenylphosphinomethyl)-1,1′-biphenyl (Tetrabi)(38 mg. 0.04 mmol) within a glove box and placing them into a complexflask, then adding deoxygenated/dewatered dichloromethane (6.63 g. 78.0mmol) in a complex flask and stirring to dissolve them to obtain acomplex solution of rhodium and biphenyl tetraphosphine ligand.Subsequently, weighing the ruthenium catalyst RuH(Cl)(PNN)(CO)(4.9 mg,0.01 mmol) within a glove box and adding it into the complexed rhodiumcatalyst solution at room temperature. Placing the autoclave into theglove box, using a micro syringe to transfer 100 μl of the complexedrhodium-ruthenium catalyst solution into a reaction flask (5 ml) withmagnetic stirrer, and adding 100 μl of the internal standard n-decane,adding 150 μl of additive and 350 μl of solvent, finally 2-octene(cis-mixture) (224.4 mg. 2 mmol). Then, taking the autoclave containingthe reaction flask out from the glove box, and replacing the high-purityargon gas in the vessel with H₂ three times, raising the total pressureof the autoclave to 4 bar at a CO/H₂ pressure ratio of 1:1, and thenplacing the autoclave at oil bath temperature 140° C. and stirring for 1hour and 4 hours, respectively.

TABLE 3

L/Rh Time conversion l/b Linearity No. solvent ligand L/Ru [h] rate[%][%] [%] TON  1 ethanol Tribi 4:1 1  8.2 12.7 92.7 8.2 × 10²  2 ethanolTribi 4:1 4 26.4 15.4 93.6 2.6 × 10³  3 ethanol Tetrabi 4:1 1 18.9 33.797.1 1.9 × 10³  4 ethanol Tetrabi 4:1 4 36.1 31.0 96.9 3.6 × 10³  5methanol Tribi 4:1 1 20.0 35.2 97.3 2.2 × 10³  6 methanol Tribi 4:1 460.8 28.4 96.6 6.1 × 10³  7 methanol Tetrabi 4:1 1 41.1 72.5 98.6 4.1 ×10³  8 methanol Tetrabi 4:1 4 79.4 58.2 98.3 7.9 × 10³  9trifluoroethanol Tribi 4:1 1 11.7 42.6 97.7 1.2 × 10³ 10trifluoroethanol Tribi 4:1 4 31.5 27.6 96.5 3.2 × 10³ 11trifluoroethanol Tetrabi 4:1 1 28.0 79.7 98.7 2.8 × 10³ 12trifluoroethanol Tetrabi 4:1 4 47.5 42.5 97.7 4.8 × 10³

Example 4: Isomerization and hydroformylation (S/C=10000) usingrhodium-ruthenium dual metal (Rh(acac)(CO)₂, RuH(Cl)(PNN)(CO)) andbiphenyl triphosphine ligand (Tribi), rhodium-ruthenium dual metal(Rh(acac)) (CO)₂, RuH(Cl)(PNN)(CO)) and biphenyl tetraphosphine ligand(Tetrabi) (comparison of various α-, β-, γ-olefin results)

Rh, Ru+Tribi: Weighing the catalyst Rh(acac)(CO)₂ (2.6 mg, 0.01 mmol),2, 2′,6-tris(diphenylphosphinomethyl)-1. 1′-Biphenyl (30 mg, 0.04 mmol)within a glove box and placing them into a complex flask, and thenadding deoxygenated/dewatered dichloromethane (1.33 g. 15.6 mmol)solvent into the flask, stirring to dissolve them to obtain a complexsolution of rhodium and biphenyl triphosphine ligand. Subsequently,weighing a ruthenium catalyst RuH(Cl)(PNN)(CO) (4.9 mg, 0.01 mmol)within a glove box, adding it to the complexed rhodium catalystsolution, and stirring at room temperature to dissolve them. Placing theautoclaves into the glove box, using a micro syringe to transfer 100 μlof the complexed rhodium-ruthenium catalyst solution into a reactionflask (5 ml) with magnetic stirrer, and adding 100 μl of the internalstandard n-decane, appropriate amount of additives and correspondingsolvents, and finally various α-, β-, γ- olefin (1 mmol) in batches.Then, taking the autoclaves containing the reaction flasks out from theglove box, and replacing the high-purity argon gas in the vessels withH₂ three times, raising the total pressure of the autoclaves to 4 bar ata CO/H₂ pressure ratio of 1:1, and then placing the autoclaves at oilbath temperature 140 ° C. and stirring for 2 hours.

Rh, Ru+Tetrabi: Weighing the catalyst Rh(acac)(CO)₂ (2.6 mg, 0.01 mmol),2′,6,6′-tetrakis(diphenylphosphinomethyl)-1,1′Biphenyl (Tetrabi) (38 mg,0.04 mmol) within a glove box and placing them into a complex flask, andthen adding deoxygenated/dewatered toluene (0.87 g, 9.4 mmol) into theflask and stirring to dissolve to obtain a complex solution of rhodiumand biphenyl tetraphosphine ligand. Subsequently, weighing a rutheniumcatalyst RuH(CI)(PNN)(CO) (4.9 mg, 0.01 mmol) within a glove box, addingit to the complexed rhodium catalyst solution, and stirring at roomtemperature to dissolve them. Placing the autoclaves into the glove box,using a micro syringe to transfer 100 μl of the complexedrhodium-ruthenium catalyst solution into the reaction flask (5 ml) withmagnetic stirrer, and adding 100 μl internal standard n-decane,appropriate amount of additives and corresponding solvents, and finallyvarious α-, β-, γ- olefin (1 mmol) in batches. Then, taking theautoclaves containing the reaction flasks out from the glove box, andreplacing the high-purity argon gas in the vessels with H₂ three times,raising the total pressure of the autoclaves to 4 bar at a CO/H₂pressure ratio of 1:1, and then placing the autoclaves at oil bathtemperature 140° C. and stirring for 2 hours.

TABLE 4

conversion l/b linearity Isomerization No. substrate ligand rate[%] [%][%] [%] TON  1 Trans-2-hexene Tribi 59.2 22.8 95.8 9.9 5.9 × 10²  2Trans-2-hexene Tetrabi 60.8 39.0 97.5 12.8 6.1 × 10²  3 Cis-2-hexeneTribi 81.9 75.9 98.7 47.3 8.2 × 10²  4 Cis-2-hexene Tetrabi 85.1 82.398.8 61.5 8.5 × 10²  5 Cis, trans-2-octene Tribi 72.5 99.0 99.0 1.8 7.3× 10²  6 Cis, trans-2-octene Tetrabi 80.4 110.1 99.1 2.6 8.0 × 10²  7Cis, Tribi 61.1 44.5 97.8 32.4 6.1 × 10² trans-2-nonylene  8 Cis,Tetrabi 82.8 65.7 98.5 64.3 8.3 × 10² trans-2-nonylene  9 Trans-3-hexeneTribi 55.2 8.4 89.4 9.5 5.5 × 10² 10 Trans-3-hexene Tetrabi 49.6 65.798.5 13.9 5.0 × 10² 11 Trans-3-octene Tribi 67.8 11.8 92.2 50.7 6.8 ×10² 12 Trans-3-octene Tetrabi 78.1 44.5 97.8 46.6 7.8 × 10² 13Cis-4-octene Tribi 64.2 10.1 91.0 48.3 6.4 × 10² 14 Cis-4-octene Tetrabi72.9 61.5 98.4 47.9 7.3 × 10² 15 Cis, trans-4-octene Tribi 46.7 4.6 82.012.1 4.7 × 10² 16 Cis, trans-4-octene Tetrabi 59.3 57.8 98.3 27.7 5.9 ×10²

What is claimed is:
 1. A catalyst comprising a rhodium complex and aruthenium compound, wherein the rhodium complex is formed by complexinga rhodium compound with a biphenyl tetraphosphine ligand.
 2. Thecatalyst according to claim 1, wherein the molar ratio of the rhodiumcomplex to the ruthenium compound is ranged from 1:1 to 5:1, and themolar ratio of the biphenyl tetraphosphine ligand to the rhodiumcompound is ranged from 1:1 to 10:1.
 3. The catalyst according to claim1, wherein the rhodium compound is selected from a group consisting of:RhCl₃, (Rh(NBD)Cl)₂, (Rh(COD)Cl)₂, (RH(ethylene)₂(CI))₂, RhCl(PPh₃)₃,(Rh(CO)₂Cl)₂ , Rh(acac)(CO)₂, Rh(acac)(COD), Rh₆(CO)₁₂, Rh₄(CO)₁₂,Rh₂(OAc)₄, Rh(NO₃)₃, (Rh(NBD)₂)X and (Rh(COD)₂)X, wherein X is aconjugated anion, NBD is a bicycloheptadiene; and COD is cyclooctadiene.4. The catalyst according to claim 1, wherein the biphenyltetraphosphine ligand has a structure illustrated as follows.

in formula 1, Ar is selected from a group consisting of: benzene,p-methylbenzene. m-trifluoromethylbenzene, p-trifluoromethylbenzene,3,5-ditrifluoromethylbenzene, 3,5-difluorobenzene, 3,5-dimethylbenzene,3,5-di-tert-butylbenzene, 3,5-di-tert-butyl-4-methoxybenzene,p-methoxybenzene, p-dimethylaminobenzene, 2-pyridine, p-fluorobenzene,and 2, 3, 4, 5, 6-pentafluorobenzene.
 5. The catalyst according to claim1, wherein the ruthenium compound is selected from a group consistingof: Ru₃(CO)₁₂, RuCl₃, RuCl₂(PPh₃)₃, (RuCl₂(CO)₃)₂, RuH(CO)₂(PPh₃)₃,Ru(Ar)X₂, Ru(ArH)Cl₂, Ru(Ar)X₂(PPh₃)₃, Ru(COD)(COT), Ru(COD)(COT)X,Ru(COD)_(n), RuCl₂(COD), (Ru(COD)₂)X, (RuCl₂(COD))_(n),Ru(COD)(methallyl)₂, RuX₂(cymene), RuX₂(PN), RuX₂(PN), RuH(CI)(PNN(CO),and RuH(PNN)(CO), wherein Ar is a group having an aromatic ring; X is aconjugated anion, COD is cyclooctadiene; and COT is cyclooctadiene.
 6. Areaction method for isomerization and hydroformylation of internalolefins, comprising: first, under inert gas protection, transferringcertain amount of a complexed rhodium-ruthenium catalyst solution,certain amount of isopropanol as an additive, certain amount of solvent,and finally a substrate-internal olefin into a reaction flask equippedwith a magnetic stirrer; second, charging certain amount of CO and H₂with a certain pressure into a autoclave containing the reaction flask,and wherein a pressure ratio of H2 to CO is ranged between 1.5:1 and10:1, and the total pressure is ranged from 0.2 MPa to 4 MPa: andplacing the autoclave at oil bath temperature between 80° C. and 140° C.and stirring for 1 to 12 hours.
 7. The reaction method according toclaim 6, wherein the organic solvent is selected from a group consistingof: methylbenzene, dichloromethane, dichloroethane, hexane, ethylacetate, methanol, ethanol, trifluoroethanol, isopropanol, dioxane,acetonitrile and tetrahydrofuran.
 8. The reaction method according toclaim 6, wherein the internal olefin is selected from a group consistingof: 2-butene, cis-trans-2-pentene, cis-trans-2-hexene,cis-trans-3-hexene, cis-trans-2-heptene, cis-trans-3-heptene,cis-trans-2-octene, cis-trans-3-octene, cis-trans-4-octene,cis-trans-2-nonene, cis-trans-3-nonene, cis-trans-4-nonene,cis-trans-2-decene, cis-trans-3-decene, cis-trans-4-decene, andcis-trans-5-decene.
 9. Use of the catalyst according to claim 1 forcatalyzing isomerization and hydroformylation of internal olefin.